The synthesis, stable existence regions, structure, and migration characteristics of complex oxides of the BIMEVOX family were studied experimentally and theoretically. The temperature, composition, and oxygen partial pressure dependences of the conductivity of the samples obtained were determined. The contribution of oxide ion transport decreased as the temperature and oxygen partial pressure lowered. Quantum-chemical calculations of β-Bi4V2O11 and γ-Bi 4V2O11 were performed to analyze the relative stabilities of the phases and the influence of dopants. © Nauka/Interperiodica 2006.